CN107240435B - A kind of photovoltaic cell silver paste and preparation method thereof - Google Patents
A kind of photovoltaic cell silver paste and preparation method thereof Download PDFInfo
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- CN107240435B CN107240435B CN201710352527.4A CN201710352527A CN107240435B CN 107240435 B CN107240435 B CN 107240435B CN 201710352527 A CN201710352527 A CN 201710352527A CN 107240435 B CN107240435 B CN 107240435B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 38
- 239000004332 silver Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 17
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 15
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 15
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 15
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 15
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000000661 sodium alginate Substances 0.000 claims abstract description 14
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 14
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims abstract description 10
- 229930195725 Mannitol Natural products 0.000 claims abstract description 10
- 239000000594 mannitol Substances 0.000 claims abstract description 10
- 235000010355 mannitol Nutrition 0.000 claims abstract description 10
- 238000007639 printing Methods 0.000 claims abstract description 10
- 239000000428 dust Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960001855 mannitol Drugs 0.000 claims abstract description 6
- 238000007650 screen-printing Methods 0.000 claims abstract description 6
- 229910020252 KAuCl4 Inorganic materials 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 6
- 235000009508 confectionery Nutrition 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052710 silicon Inorganic materials 0.000 abstract description 15
- 239000010703 silicon Substances 0.000 abstract description 15
- 238000005245 sintering Methods 0.000 abstract description 10
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 23
- 239000002002 slurry Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 8
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- -1 copper citrate gold Chemical compound 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000989 Alclad Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229940071575 silver citrate Drugs 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Sustainable Energy (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Conductive Materials (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a kind of photovoltaic cell silver paste and preparation method thereof, silver paste includes following component：Conductive phase 50 70%, glass dust 10 25%, organic carrier 10 25%, additive 1 3%；Ratio above is mass percent；Wherein, conductive phase is the mixture of silver powder and the silver medal of citric acid three.Additive is TiO2Or KAuCl4With microcrystalline cellulose, sodium alginate, mannitol any mixture；（1）Conductive phase and glass dust are added to the mixture of absolute ethyl alcohol and ethylene glycol；（2）Take organic carrier uniformly to be mixed with organic solvent, and ground and rolled with three-roll grinder；（3）Silverskin is prepared using silk-screen printing technique；（4）The silverskin of printing is placed in Muffle furnace, calcined at 700 800 DEG C under 3 5s.The printing performance that the present invention has had, and it is small with the contact resistance of silicon chip, electrode width is narrow after sintering, and thickness is high, and compactness is good, greatly reduces silver powder dosage, and overall cost is low.
Description
Technical field
The present invention relates to a kind of unleaded photovoltaic cell silver paste and preparation method thereof, sintering temperature is low, and printing is good.
Background technology
With deepening continuously for solar cell research and development, solar cell steps into the commercial application stage substantially.Mesh
Preceding in the market solar cell material is mainly silicon systems solar cell, including crystalline silicon, polysilicon and the polysilicon membrane sun
Energy battery, silicon-based film solar cells etc..The electrode for being produced on battery plane of illumination is referred to as Top electrode, is produced on cell backside
Electrode is referred to as bottom electrode or back electrode.Top electrode is negative pole, be with silver conductive paste by being screen printed onto on antireflective coating,
Electrode is formed through oversintering.Bottom electrode is positive pole, is made up of aluminium paste and silver-colored aluminium paste, and wherein aluminium paste is silicon solar cell anode
Slurry.Important component of the front electrode as solar cell, it is main to play collected current, while to battery by
Light area and series resistance have conclusive influence.
Crystal silicon solar energy battery front conductive silver slurry is mainly by conductive phase, inorganic binder, organic carrier and addition
The three parts raw material such as agent is formulated.Entirety requires：1st, good Ohmic contact, low contact resistance can be formed；2nd, have excellent
Line conductance, stronger adhesion strength, high aspect ratio, wide sintering process window；Chemical stability is good, there is solderability, resistance to weldering
Property and adhesive force.Conductive phase can select the good metal dusts of electrical and thermal conductivity performance such as Au Ag Pt Pd, and it is total to typically constitute from slurry
The 80%~90% of amount.Because silver powder has a good electrical and thermal conductivity performance, and for other noble metals, price is just
Preferably, it is widely used as the conductive phase of electrocondution slurry.If silver powder too high levels (>90%) probability of connected resin parcel is low,
The cohesive force of silver conductor declines after film forming, and silver granuel has the danger to come off, but silver content is less than 60%, then the change of resistance is unstable
It is fixed.Silver powder is the chief component of silver paste, ultimately forms the conductive layer of electrode, its particle diameter, shape, surface state, compares surface
Product etc. all has a great impact to the performance of slurry, and particle diameter is excessive, and the viscosity and stability of silver paste are significantly reduced, particle diameter mistake
It is small, it is easy to aoxidize, it is difficult to mix with other components.Inorganic binder is glass dust, mainly oxide (PbO, B2O3, SiO3,
ZnO3) powder, the inorganic phase of solidify afterwards fluxing action is heat-treated, accounts for the 5-10% of slurry；It decides electrocondution slurry to the sun
The energy penetration capacity of battery antireflective film and the adhesion of electrode pair silicon chip, and inorganic binder is to ohmic contact resistance
Play an important role.Organic carrier is mainly made up of organic solvent, macromolecule resin and portions additive etc., and main function is to confer to
The certain printing of slurry and storage property, typically constitute from the 5%~15% of slurry total amount.
Publication No. 102426873B patent document discloses a kind of silicon solar cell positive silver paste and its preparation side
Method, reduction silver paste production cost is can aid in by adding alloyed powder in electrocondution slurry, while improve leading for electrocondution slurry
Electrical property, therefore the solar cell for making finally to be prepared has higher electricity conversion.Its add alloyed powder be
Silver-colored phosphor copper powder, main starting point still reduce silver powder dosage, reduce cost.
Publication No. 106297954A patent document discloses a kind of electrode slurry used for solar batteries and its preparation side
Method, using zinc flake, spherical copper powder 5-10 parts, silver-colored alclad alloyed powder, lithium iron phosphate/carbon nano-fiber composite material as raw material,
It can form that adhesive force is strong, cell photoelectric high conversion efficiency in solar cell surface.
Publication No. 102324263A patent document discloses a kind of silver paste for solar cell and its preparation side
Method, the purpose is to provide a kind of lead-free silver paste, lead-free glass powder is mainly employed, include 75%-80% silver powder, added
Agent is using cellulose, and such as the one or more in ethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose, silver powder contains
Amount is high, and overall cost is high.
Publication No. 102324263A patent document discloses a kind of composition for electrode formation, is divided in decentralized medium
Dissipating has the composition for electrode formation of metal nanoparticle, and wherein metal nanoparticle contains more than 75% Nano silver grain,
And describe to reduce the roughness on the surface to form electrode, it is necessary to add additive, such as silver citrate, copper citrate gold
Belong to soaps (specification [0058], [0061] section), but overall cost is still very high.
Publication No. 101523509A patent document discloses conductive layer formation slurry, but the conductive layer master described in it
If conductive pattern, touch-screen as the flat-panel monitor such as LCD (liquid crystal display) and PDP (PDP)
Electrode, the PAD electrodes of plane fluorescent lamp backlight, the argent in the slurry, it is with silver aliphatic carboxylate to have 0.1-90%
Form exist, 1-60% be in the form of silver powder exist, its examine parameter in addition to resistance, also to evaluate conductive pattern,
Operation temperature etc..
Publication No. 101271928A patent document, disclose a kind of high-viscosity solar cell front side silver paste and its system
The conductive silver powder content of Preparation Method, the wherein silver paste is 75-85%, there is also same overall cost it is high the problem of.
Therefore, there are still larger with import in terms of electric conductivity and Stability of Slurry for overall domestic conductive silver slurry
Gap, how on the premise of cost is ensured the excellent silver paste of production performance is still a problem.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of unleaded photovoltaic cell silver paste, tool
The printing performance having had, and (can effectively permeate antireflection layer) small with the contact resistance of silicon chip, electrode width is narrow after sintering, thickness
Height, compactness is good, greatly reduces silver powder dosage, and overall cost is low.
It is another object of the present invention to provide a kind of preparation method of unleaded photovoltaic cell silver paste, than traditional burning
Junction temperature reduces, and more saves.
In order to realize foregoing invention purpose, present invention employs following technical scheme：
A kind of photovoltaic cell silver paste, including following component：It is conductive phase 50-70%, glass powder 10-25%, organic
Carrier 10-25%, additive 1-3%；Ratio above is mass percent.
Wherein, conductive phase is silver powder, and additionally with the addition of the silver medal of citric acid three, and the silver medal mass ratio of citric acid three is 1-5%, silver
Powder content is more preferably 60-70%.
In terms of electric conductivity, in the range of 50-70%, with the increase of silver powder content, the conducting particles in slurry increases,
Sintering film resistivity will decline, and when silver powder content reaches 70%, if continuing to add silver powder, resistivity does not continue to subtract
Small, but have rising by a small margin, because the content of silver powder is excessive, the relative amount of glass dust is reduced so that silver powder it
Between bond variation, the Forming ability of conductive path is deteriorated.After with the addition of the silver medal of citric acid three, the agglutinating property of silver paste improves, silver
Ion is easier to be combined with Si, glass, and reduces the dosage of silver powder.
Described silver powder is ball shape silver powder or flake silver powder, preferably ball shape silver powder；Silver powder is two kinds of particle size ranges
Mixture, the i.e. mixture of 10-30 nanometers and 70-100 nano-silver powders；Traditionally, silver powder particles increase, cell contact resistance
Reduced with series resistance, the present invention is using the silver powder mixing of two kinds of particle diameters, tap density 5.5g/m3, the contact resistance of battery
Small, sintering character is good.
Additive is TiO2Or KAuCl4, dosage 0.5-1.5%, and with microcrystalline cellulose, sodium alginate, sweet dew
Any mixture of alcohol, dosage 0.5-1.5%.
Glass powder plays a part of cohesive substrate and electrode in sintering process, its softening point, particle diameter and its in slurry
In content the solderability, tack, bond strength of electrode can be had an impact.Additive TiO2Or KAuCl4Granularity be
Micron order, in cooling procedure, play a part of Nucleating Agent in glass, due to the controlled micro crystallization of glass, dissolving silver is in glass phase
Middle degree of supersaturation increase, the crystallization silver quantity increase of precipitation, also provides more sections, adds the contact point and tunnel of conduction
Channel effect, contact resistance diminish.
The solution of organic carrier polymer in organic solvent, determine paintability (such as silk-screen printing of electric slurry
Deng), polymer is generally cellulose family, resin polymers, and it can use ethyl cellulose, acrylic resin, nitrocellulose
One or more in element, phenolic resin.Its effect is powder is uniformly dispersed, and forms the liquid of slurry, has slurry
Suitable viscosity, volatility, thixotropy and levelability, inventor organic carrier with the addition of microcrystalline cellulose, sodium alginate or
Person's mannitol, addition 0.5-1.5%；Most preferably, dosage 1.0%, in the range of 0.5-1.0%, with microcrystalline cellulose
The increase of element, sodium alginate or mannitol, silver powder grows into speed and the adhesion increase of silicon face, in 1.0-1.5 scopes
Inside then conversely, reach optimal when addition is 1.0%, and the thixotropy of slurry is improved, improve printing.From principle
On say, inventor not only greatly reduces containing for silver powder surprisingly it has been found that addition microcrystalline cellulose, sodium alginate or mannitol
Amount, and in electrode sintering process, frit becomes liquid, dissolves silver powder, is corroded through ARC, and in silicon and oxidation
In redox reaction between thing, glass, micro microcrystalline cellulose helps silver powder and grows into silicon face, but more than the present invention
The addition of ratio can weaken the speed that silver powder grows into silicon face on the contrary.
A kind of preparation method of photovoltaic cell silver paste, step are as follows：
(1) conductive phase silver powder and inorganic phase glass dust are added the 1 of absolute ethyl alcohol and ethylene glycol：1 mixture mixing, is obtained
Solid powder；
(2) take solid powder uniformly to be mixed with organic carrier, and additionally add microcrystalline cellulose, sodium alginate or sweet dew
Alcohol it is any,
(3) silverskin is prepared using silk-screen printing technique；
(4) silverskin of printing is placed in Muffle furnace, forged under sintering temperature and soaking time (700-800 DEG C/3-5s)
Burn.
Brief description of the drawings
Fig. 1 is the electron microscope that the gained silver paste of the embodiment of the present invention 3 is sintered in Si planes of crystal, it can be seen that Ag powder into
Grow into silicon face work(.
Embodiment
Technical scheme is illustrated below with reference to embodiment：
The glass dust of following examples is using (Bi2O3-B2O3-ZnO systems)
Component and content are as shown in table 1 used by embodiment 1-5：
Table 1
Preparation method is as follows used by embodiment in table 1：
(1) the spherical silver powder of conductive phase or flake silver powder are added the 1 of absolute ethyl alcohol and ethylene glycol with inorganic phase glass dust：1
Mixture is mixed to get solid powder；
(2) take solid powder uniformly to be mixed with organic carrier, and additionally add microcrystalline cellulose, sodium alginate or sweet dew
Alcohol it is any, and ground and rolled with three-roll grinder；
(3) silverskin is prepared using silk-screen printing technique；Present invention employs the screen printing sizing agent of 350 mesh numbers, and by institute
Slurry is screen printed onto and is coated with reflectance coating SiNx monocrystalline silicon piece, the temperature of 180 degrees centigrades dries 10min；
(4) silverskin of printing is placed in Muffle furnace, forged under sintering temperature and soaking time (700-800 DEG C/3-5s)
Burn.
Organic carrier employed in the present invention is the dibutyl phthalate for thickener with ethyl cellulose 5%
25%+ ATBC 25%+ terpinol 25%+ dimethylbenzene 25% is prepared for solvent, because only with ethyl cellulose
Bad for the slurry printing performance of thickener, inventor with the addition of microcrystalline cellulose, sodium alginate or mannitol, preferably gram
The defect has been taken, but used in amounts will be controlled strictly, and from the experimental results, using sodium alginate or mannitol as additive,
Effect is better than microcrystalline cellulose, and it is more excellent to be embodied in photoelectric conversion effect.
The unit for electrical property parameters that monocrystaline silicon solar cell piece is prepared using the slurry of the present invention is as shown in table 2：
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Ipm/A | 5.198 | 5.071 | 4.978 | 5.012 | 5.467 |
| Vpm/A | 0.500 | 0.518 | 0.499 | 0.512 | 0.501 |
| Rs/Ω | 0.024 | 0.023 | 0.022 | 0.023 | 0.022 |
| Rsh/Ω | 10.645 | 11.543 | 10.732 | 9.567 | 10.997 |
Table 2 is visible, and the short circuit current of obtained solar cell is very big, and series resistance is very big, and photoelectric transformation efficiency is very high.
In the case of ceteris paribus, change additive microcrystalline cellulose, sodium alginate, mannitol to battery performance
Influence such as embodiment 6 (table 3,4), it is seen that additive the resistance or silver powder of resultant battery are grown into the speed oil of silicon face compared with
It is big to influence.
The influence experiment of the additive microcrystalline cellulose of embodiment 6, mannitol, sodium alginate
Table 3
Table 4
Claims (5)
1. a kind of photovoltaic cell silver paste, it is characterised in that including following component：Conductive phase 50-70%, glass dust 10-
25%th, organic carrier 10-25%, additive 1-3%；Ratio above is mass percent；
Wherein, conductive phase is the mixture of silver powder and the silver medal of citric acid three, and the silver medal mass ratio of citric acid three is 1-5%；
Additive is TiO2Or KAuCl4With microcrystalline cellulose, sodium alginate, mannitol any mixture.
2. photovoltaic cell silver paste according to claim 1, it is characterised in that described silver powder is ball shape silver powder or piece
Shape silver powder.
3. photovoltaic cell silver paste according to claim 1, it is characterised in that silver powder is 10-30 nanometers and 70-100 nanometers
The mixture of silver powder；Tap density is 5.5g/m3。
4. photovoltaic cell silver paste according to claim 1, it is characterised in that in additive, TiO2Or KAuCl4Use
Measure as 0.5-1.5%, the dosage of microcrystalline cellulose, sodium alginate or mannitol is 0.5-1.5%.
5. the preparation method of the photovoltaic cell silver paste described in claim 1-4, it is characterised in that step is as follows：
Step (1), conductive phase and glass dust added the 1 of absolute ethyl alcohol and ethylene glycol：1 mixture mixing, obtains solid powder；
Step (2), take solid powder uniformly to be mixed with organic carrier, and additionally add microcrystalline cellulose, sodium alginate or sweet
Reveal any of alcohol, and ground and rolled with three-roll grinder；
Step (3), using silk-screen printing technique prepare silverskin；
Step (4), the silverskin of printing is placed in Muffle furnace, 3-5s is calcined at 700-800 DEG C.
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| CN110047611B (en) * | 2019-04-18 | 2021-06-01 | 北京元六鸿远电子科技股份有限公司 | Conductive silver paste for low-temperature sintering LTCC |
| CN110459343B (en) * | 2019-06-19 | 2020-12-18 | 南通天盛新能源股份有限公司 | Low-temperature sintering type back silver paste for all-aluminum back surface field crystalline silicon solar cell |
| CN114005574B (en) * | 2021-11-11 | 2023-09-26 | 中国有色桂林矿产地质研究院有限公司 | High-temperature electronic paste doped with ammonium alginate biphenyl paste and preparation method thereof |
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